This invention relates to the use of 1-nonen-3-ol as a repellent for house flies (Musca domestica) and further it relates to materials suitable for candle bodies which candle bodies include compositions of matter which are both (i) efficaciously insect repelling and (ii) perfuming in an aesthetically pleasing manner on use thereof. This invention also relates to apparatus useful in determining the repellency of molecules including said 1-nonen-3-ol comprising:
(i) active and passive insect interest visual or electronic measuring and recording means which may, optionally, be connected to an electric power supply source; PA1 (ii) enclosed insect feeding and/or stimulating means having controlled limited access to the external environment surrounding said apparatus and associated with said measuring and recording means, said insect feeding and/or stimulating means being located at a fixed insect feeding and/or stimulating means location defined according to x, y and z coordinates having a defined first 3-space, said insect feeding and/or stimulating means consisting essentially of: PA1 (iii) optionally, steady-state direct lighting means for supplying a beam of direct light having a given substantially constant intensity or intensities and wavelength or wavelengths to said feeding and/or stimulating means location; and PA1 (iv) steady state air supply, air conduction and air removal means for supplying, conducting and removing air at a substantially constant mass flow rate and substantially constant linear velocity to, past and from a second 3-space immediately above said insect feeding and/or stimulating surface (simultaneously, if appropriate, with the supplying of the beam of direct light to said feeding and/or stimulating means location substantially immediately above said insect feeding and/or stimulating surface) said insect feeding and/or stimulating surface structure, optionally, being constructed so that said measuring and recording means is sensitive to the completion of a circuit of electron flow through or proximate said conductive elements of said insect feeding and/or stimulating surface, whereby the number and frequency of the insects attracted (if appropriate, relative to the attractancy of said direct lighting means) to the proximity of said feeding and/or stimulating means is capable of being determined either (a) using said measuring and recording means or (b) visually. PA1 (a) Perfuming to the environment surrounding the PA1 (b) Adequately insect repellent to the environment surrounding the material at various environmental temperatures at atmospheric pressure, from a temperature of about 0.degree. C. up to a temperature of about 50.degree. C. PA1 (a) From about 35% up to about 85% by weight of an oil which is normally liquid at room temperature which may be light mineral oil and a natural oil; PA1 (b) From about 7% up to 40% by weight of a long chain polyamide having a molecular weight between 6,000 and 9,000 and a softening point within the range of 185.degree. C.-48.degree. C. from about 7% up to about 30% by weight of an alcohol which may be a C.sub.8 up to a C.sub.12 primary alcohol. PA1 "The inclusion in the composition of certain alcohols that produce otherwise desirable properties may result in a material that burns with an acrid or pungent odor. In such cases a small amount of an odor masking agent can be incorporated in the composition. The material sold by Fritzche, Dodge and Olcott as its No. 41984 has been found satisfactory when incorporated in the composition in amounts up to about 0.2 percent by weight. The odor-masking agent is desirable when less expensive alcohols are used and may be unnecessary if the alcohols are highly refined, but from the standpoint of cost, the use of the cheaper alcohols and an odor-masking agent is indicated and produces satisfactory results. If desired, a small amount of perfume can be added to the composition to complete the odor-masking effect." PA1 "Insect repellent contains benzalacetone (I) as active component. (I) has an immediate effect used in combination with sublimating substance such as naphthalene and camphor. The ratio of blend of benzalacetone to the sublimating substance is 90:1-5:95. Optionally, an excipient such as silica gel, talc and binder such as PVA or CMC and aromatic substance can be added (I) can be put in a suitable vessel, can be prepared as as tablet, or can be supported on cloth or paper. PA1 Benzalacetone has the melting point of 41.degree.-42.degree. C. and the boiling point of 260.degree.-262.degree. C. The saturated gas concentration of benzalacetone is 0.045 mg/1 by gas chromatography and is one tenth that of laevo-carvone and one third that of thymol, and therefore it has long-lasting effect. PA1 (I) is nontoxic to warm-blooded animals, and shows repelling effect for a long period of time. It is prepared in low cost, and can be stored in a plastic vessel, since it does not etch plastics. It is particularly effective in the repellin of insects for clothes, e.g., Tinea pellionella."
(a) an insect feeding and/or stimulating surface which may, optionally, comprise at least two spaced electrically conductive elements PA2 (b) immediately beneath said insect feeding and/or stimulating surface a composition of matter comprising molecules to be tested for attractancy and repellency; PA2 (c) immediately beneath said molecules to be tested, a feeding stimulant composition or a stimulant composition for said insects;
(i) connected to said measuring and recording means; and PA3 (ii) capable of forming a complete circuit, said elements having such dimensions and spacing from one-another as to cause an attracted insect to complete a circuit of electron flow through or proximate to said elements;
This invention also relates to a process using such apparatus for determining the repellency of molecules including said 1-nonen-3-ol.
Formulations exist in commerce which are said to provide adequate insect repellent properties, e.g., those set forth in U.S. Pat. No. 2,043,941 which indicate the repellency properties of methallyl disulfide having the structure: ##STR1## and those set forth in U.S. Pat. No. 4,449,987 issued on May 22, 1984 which indicate the combination of methyl heptenones, coumarin and indole for use in perfumed candles.
However, efficacious compositions of matter taken alone or for use in combination with perfumes for repelling house flies have not yet been developed.
Unsaturated alcohols and esters thereof are known with respect to controlling insects; however, they have been found to attract rather than repel such insects. Thus, U.S. Pat. No. 4,152,422 issued on May 1, 1979 sets forth 6-nonen-1-ol in a composition of matter used as an attractant for the male Mediterranean Fruit Fly. Chem. Abstracts Volume 103, No. 71086p concerns the synthesis of (Z)-8-dodecen-1-ol and its acetate as pheromone components of the Oriental Fruit Moth (Grapholita molesta). This is an abstract of the article in Acta Chem. Scan Ser. B., 1985, B39(4), pages 267-72. U.S. Pat. No. 4,364,931 issued on Dec. 21, 1982 discloses the use of 9(Z)-tetradecen-1-ol acetate in attracting male white-line dart moths.
Chem. Abstracts Volume 80, 1974, at No. 117098f discloses the use of trans-6-nonen-1-ol acetate as an ovipositional attractant and stimulant of the melon fly. U.S. Pat. No. 2,254,665 issued on Sep. 2, 1941, on the other hand, discloses the use of aliphatic alcohols in general in repelling insects which aliphatic alcohols have from 10 to 14 carbon atoms. Examples of the aliphatic alcohols of U.S. Pat. No. 2,254,665 are all saturated, to wit:
dodecyl alcohol; PA0 octol alcohol; PA0 hexadecyl alcohol; PA0 tetradecyl alcohol; and PA0 undecyl alcohol.
U.S. Pat. No. 2,254,665 fails to disclose the use of unsaturated alcohols in insect repellent compositions.
Chem. Abstracts Volume 74, 1971 at No. 99419f discloses various nonenyl acetates as attractants for female melon flies (abstract of J. Med. Chem., 1971, 14(3), pages 236-9 including trans-2-nonen-1-yl acetate.
Formulations exist in commerce which are said to provide candle body materials that are both perfuming and insect repellent but such formulations have yielded a candle body that is either insufficiently insect repellent or aesthetically displeasing from an organoleptic standpoint.
When a candle burns, the heat of its flame melts a small pool of the candle body material around the base of the exposed portion of the wick, and this molten material is drawn up through the wick by capillary attraction to fuel the flame. Thus, the process that takes place in the burning of a candle imposes rather stringent functional requirements upon the candle body material.
The material of a candle body must be rigid enough to support itself and a relatively long wick filament, but it should not be excessively brittle at low temperatures. Its melting point is critical in that it should liquify temperatures, to which, it can be raised by radiant heat from the candle flame. If its melting temperature is too low, the candle will drip or, in an extreme case, the entire candle body will melt, dropping the wick into a pool of molten material with the hazardous possibility that the surface of the pool will ignite when this happens. If too high a temperature is required to melt the body material, the flame will be starved because insufficient fuel will be drawn up through the wick, with the result that the flame will be too small to maintain itself. When molten, moreover, the candle body material must have a relatively low viscosity in order to insure that it will be capable of being drawn up through the wick by capillary action.
In addition to meeting these requirements the candle body material must burn with a flame that is both luminous and smokeless and such odors as are produced by its combustion should not be unpleasant and should preferably be faint.
The functional requirements outlined above have, of course, been met by various candle body materials that are well known in the art, but heretofore no known materials that meet these requirements has been both:
burning candle; and
However, the desire for such a candle body material which is either transparent, opaque or translucent has long persisted where the candle composition is both insect repellent and perfuming on use.
An article by Burton, "Intrinsic mosquito repellency values of some chemical compounds" appearing in Volume 84, American Perfumer and Cosmetics, April 1969 at page 41, indicates that coumarin has a value of from 0.001 up to 0.003 micromoles per liter of air for 90% insect repulsion. It further states that indole has a property such that 0.004 up to 0.01 micromoles per liter of air of Indole are needed for 90% insect repulsion. On the other hand, the article by Burton indicates that a compound such as linalool requires 0.1 micromoles per liter of linalool per liter of air for 90% insect repulsion.
Nothing is stated in the Burton article which causes one to be taught that coumarin and indole taken in combination can be added to citronella oil or one or more methyl heptenones whereby the efficacy of the overall composition is maintained or increased and the overall concentration of insect repelling mixture is substantially diminished while at the same time causing an aesthetically pleasing aroma to be emanated from the burning candle on use.
Currently on the market are "citronella oil candles" containing approximately 1.5-3% citronella oil. On use these candles give off an essentially aesthetically displeasing aroma and are not quite effective in repelling insects as desired by the user.
U.S. Pat. No. 3,615,289 issued o Oct. 26, 1971 discloses candle compositions which may be transparent or pastel shaded which are adapted to incorporate perfumes without flashing during burning, and such compositions comprise as the basic components the mixture of (i) a thermoplastic polyamide resin formed from linoleic acid polymerized with a polyamine compound; (ii) an alkanol amide or alkanol amine; and (iii) a stearic acid compound. More specifically, U.S. Pat. No. 3,615,289 specifically discloses and claims a candle composition comprising about 15 to 35% by weight of a solid gel thermoplastic polymer which is a solid polyamide resin which is the soluble condensation product of an aliphatic dicarboxylic acid and an amine, the carboxyl and amino groups of adjacent mono units being condensed to an amide linkage in the polymer (and the resin may also be based on carboxylic and amine compounds having more than two carboxyl and amino groups respectively). At column 3, line 10 of U.S. Pat. No. 3,615,289 it is indicated that the candle contain about 0.4% by weight of a perfume material. Claim 3 at column 4 of U.S. Pat. No. 3,615,289 discloses a composition wherein 5 to 7% of the composition is replaced by a coumarin-indene copolymer resin. The insect repellency of compositions usable in U.S. Pat. No. 3,615,289 is not disclosed however.
U.S. Pat. No. 3,645,705 discloses a transparert candle body composition of matter which can contain:
At column 3, line 56 of U.S. Pat. No. 3,645,705 it is disclosed that an odor masking agent may be incorporated into the candle composition. Generally this disclosure is set forth at lines 30-44 of U.S. Pat. No. 3,645,705 thusly:
Nothing in U.S. Pat. No. 3,645,705, however, discloses the applicability to the composition disclosed therein of insect repellent materials. Nothing discloses the use of a composition of matter in U.S. Pat. No. 3,645,705 which will be both a perfumant and an insect repellent.
U.S. Pat. No. 4,051,159 issued on Sept. 27, 1977 discloses a "shaped, self-supporting transparent fragrance emitting article comprising a high percentage of a thermoplastic polyamide resin having substantially uniformly dispersed therein a C.sub.14 -C.sub.22 alkyl alcohol and a fragrance emitting material". U.S. Pat. No. 4,051,159 however, does not indicate that the compositions of matter disclosed therein are useful for the purposes of candles and particularly are useful for fragrant candles or insect repellent candles or candles which are both fragrance emitting and insect repellent.
Published Japanese patent application No. J57088-101 assigned to the Agency of Industrial Sci. Tech. of Japan discloses the use of benzal acetone, laevo-carvone and thymol as insect repelling materials contained in conjunction with an aromatic substance, silica gel, talc or a binder such as polyvinyl alcohol or carboxymethyl cellulose.
Published Japanese patent application No. J 57088-101 however, does not indicate that compositions of matter are useful for the purposes of candles and particularly, are useful for fragrant candles or insect repellent candles which are both fragrancy emitting and insect repellent in an efficacious manner. The abstract of published Japanese patent application No. J 57088-101 is as follows:
Furthermore, both humans and animals are annoyed by insects and this problem is so acute as to render certain regions essentially uninhabitable by man. Disregarding the annoyance, insect bites are often accompanied by profound and in some cases serious physiological effects. Many diseases, particularly those of tropical origin, are transmitted by means of insect bites. In spite of man's constant warfare against insects they still occur in large numbers and they continue to plague both man and animals. Insecticide chemists have devoted considerable time and effort to this problem. Thousands of compounds have been tested for their toxic effect upon insects. These compounds either act as stomach poisons or respiratory paralyzers and are effective in a number of instances.
Another approach to the problem, which has also been given considerable thought, is the development of substances which have a repellent effect upon the insects. These substances can be applied upon the host in a variety of manners and serve to prevent attacks by insects which under normal conditions are attracted to these individuals.
Toxicity and repellency are not usually correlated, and it does not follow that a substance toxic to the insect is in any way repellent to it. On the other hand materials that are repellent to insects are not generally toxic and in a number of cases effective repellents are actually harmless to insects.
In order to be effective for this purpose the substance must of course, possess a high degree of repellency. In addition they must not be toxic or harmful to the individual treated. In general, it is believed that repellents are irritating to the sensory mechanism of the insect. It does not follow that a substance possessing this sensory irritating effect upon insects has a similar effect upon humans or animals. In a number of instances substances which definitely repel insects are pleasing to man and substances repugnant to man are attractive to insects.
Nothing in the prior art, however, discloses the use of 1-nonen-3-ol having the structure: ##STR2## in repelling house flies (Musca domestica) or even infers that 1-nonen-3-ol has the highly efficacious ability to repel house flies (Musca domestica), and nothing in the prior art discloses olfactometry apparatus useful in measuring such aforesaid properties.
Indeed, the literature teaches away from our invention as exemplified in "Materials Tested as Insect Attractants" compiled by M. Berazo and N. Green in Agriculture Handbook No. 239 in Table 2 wherein it is stated that 3-methyl-1-nonen-3-ol (a homologue of 1-nonen-3-ol) has on a scale of 1 to 3 an attractancy of "1" for the Oriental Fruit Fly and an attractancy of "1" for the Mediterrean Fruit Fly and 4,8-dimethyl-7-nonen-4-ol has on a scale of 1 to 3 an attractancy of "2" for the Oriental Fruit Fly and an attractancy of "3" for the Mediterrean Fruit Fly and an attractancy of "1" for the Mexican Fruit Fly and an attractancy of "1" for Drosophila. With respect to any of the nonenol derivatives set forth therein the USDA Agriculture Handbook 239 indicates that the nonenol derivatives are neither attractants nor repellents for house flies (that is Musca domestica).
Various prior art techniques for studying feeding habits of insects have been found useful in formulating processes and apparatus for determining relative attractancy and repellency for insects. Thus, the paper "Laboratory Blood Feeding of Culicoides mississippiensis (Diptera:Ceratopogonidae) Through A Reinforced Silicone Membrane" by Davis, Butler, Roberts, Reinert and Kline (J. Med. Entomol. Vol 20, No. 2: 177-182) discloses the preparation and use of a durable silicone membrane for feeding Culicoides mississippiensis in the laboratory. Further, the paper entitled "IN VITRO Feeding of Ornithodoros Ticks For Rearing And Assessment of Disease Transmission", Butler, Hess, Endris and Holscher, ACAROLOGY VI, Volume 2, published 1984 by Ellis Horwood Limited, Market Cross House, Cooper Street, Chichester, West Sussex, PO 19 lEB, England discloses the advantages of feeding of haematophagous arthropods through artificial membranes. A number of preferred embodiments of our invention includes the use of the teachings of the aforementioned papers. Accordingly, the aforementioned papers are incorporated herein by reference.